S-oxygenation of thiocarbamides. 3. Nonlinear kinetics in the oxidation of trimethylthiourea by acidic bromate

The oxidation of trimethylthiourea (TMTU) by acidic bromate has been studied. The reaction mimics the dynamics observed in the oxidation of unsubstituted thiourea by bromate with an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3, thus 4BrO(3)- + 3R(1)R(2)C=S+ 3H(2)O --> 4Br- + 3R(1)R(2)C=O + 3SO(4)(2-) + 6H+. This substituted thiourea is oxidized at a much faster rate than the unsubstituted thiourea. The oxidation mechanism of TMTU involves initial oxidations through sulfenic and sulfinic acids. At the sulfinic acid stage, the major oxidation pathway is through the cleavage of the C-S bond to form a reducing sulfur leaving group, which is easily oxidized to sulfate. The minor pathway through the sulfonic acid produces a very stable intermediate that is oxidized only very slowly to urea and sulfate. The direct reaction of aqueous bromine with TMTU was faster than reactions that form bromine, with a bimolecular rate constant of (1.50 +/- 0.04) x 10(2) M(-1) s(-1). This rapid reaction ensured that no oligooscillatory bromine formation was observed. The oxidation of TMTU was modeled by a simple reaction scheme containing 20 reactions.     

S-oxygenation of thiocarbamides IV: Kinetics of oxidation of tetramethylthiourea by aqueous bromine and acidic bromate

The kinetics and mechanism of oxidation of tetramethylthiourea (TTTU) by bromine and acidic bromate has been studied in aqueous media. The kinetics of reaction of bromate with TTTU was characterized by an induction period followed by formation of bromine. The reaction stoichiometry was determined to be 4BrO(3)(-) + 3(R)(2)C═S + 3H(2)O → 4Br(-) + 3(R)(2)C═O + 3SO(4)(2-) + 6H(+). For the reaction of TTTU with bromine, a 4:1 stoichiometric ratio of bromine to TTTU was obtained with 4Br(2) + (R)(2)C═S + 5H(2)O → 8Br(-) + SO(4)(2-) + (R)(2)C═O + 10H(+). The oxidation pathway went through the formation of tetramethythiourea sulfenic acid as evidenced by the electrospray ionization mass spectrum of the dynamic reaction solution. This S-oxide was then oxidized to produce tetramethylurea and sulfate as final products of reaction. There was no evidence for the formation of the sulfinic and sulfonic acids in the oxidation pathway. This implicates the sulfoxylate anion as a precursor to formation of sulfate. In aerobic conditions, this anion can unleash a series of genotoxic reactive oxygen species which can explain TTTU's observed toxicity. A bimolecular rate constant of 5.33 ± 0.32 M(-1) s(-1) for the direct reaction of TTTU with bromine was obtained.     

Kinetics and mechanism of bromate-bromide reaction catalyzed by acetate

The initial rate of the bromate-bromide reaction, BrO3- + 5Br- + 6H+ --> 3Br2 + 3H2O, has been measured at constant ionic strength, I = 3.0 mol L(-1), and at several initial concentrations of acetate, bromate, bromide, and perchloric acid. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm) by the stopped-flow technique. A very complex behavior was found such that the results could be fitted only by a six term rate law, nu = k1[BrO3-][Br-][H+]2 + k2[BrO3-][Br-]2[H+]2 + k3[BrO3-][H+]2[acetate]2 + k4[BrO3-][Br-]2[H+]2[acetate] + k5[BrO3-][Br-][H+]3[acetate]2 + k6[BrO3-][Br-][H+]2[acetate], where k1 = 4.12 L3 mol(-3) s(-1), k2 = 0.810 L4 mol(-4) s(-1), k3 = 2.80 x 10(3) L4 mol(-4) s(-1), k4 = 278 L5 mol(-5) s(-1), k5 = 5.45 x 10(7) L6 mol(-6) s(-1), and k6 = 850 L4 mol(-4) s(-1). A mechanism, based on elementary steps, is proposed to explain each term of the rate law. This mechanism considers that when acetate binds to bromate it facilitates its second protonation.     

pH oscillations in the BrO3--SO3(2-)/HSO3- reaction in a CSTR

Large-amplitude pH oscillations have been measured during the oxidation of sulfur (IV) species by the bromate ion in aqueous solution in a continuous-flow stirred tank reactor in the absence of any additional oxidizing or reducing reagent. The source of the oscillation in this simple chemical reaction is a two-way oxidation of sulfur (IV) by the bromate ion: (1) the hydrogen-ion-producing self-accelerating oxidation to sulfur (VI) (SO4(2-)), and (2) a hydrogen-ion-consuming oxidation to sulfur (V) (S2O6(2-)). In such a way, both the H+-producing and H+-consuming composite processes required for a pH oscillator take place in parallel in a reaction between two reagents in this system. A simple reaction scheme, consisting of the protonation equilibria of SO3(2-) and HSO3-, the oxidation of HSO3- and H2SO3 by BrO3- to SO4(2-), and the oxidation of H2SO3 to S2O6(2-) has successfully been used to simulate the observed dynamical behavior. Simulation with this simple scheme shows that oscillations can be calculated even if only about 1% of sulfur (IV) is oxidized to S2O6(2-) along with the main product SO4(2-). Agreement between calculated and measured dynamical behavior is found to be quite good. Increasing temperature decreases both the period length of oscillations in a CSTR and the Landolt time measured in a closed reactor. No temperature compensation of the oscillatory frequency is found in this reaction.     

Kinetics and mechanism of the oxidation of 4‐methyl‐3‐thiosemicarbazide by acidic bromate

The oxidation of 4‐methyl‐3‐thiosemicarbazide (MTSC) by bromate and bromine was studied in acidic medium. The stoichiometry of the reaction is extremely complex, and is dependent on the ratio of the initial concentrations of the oxidant to reductant. In excess MTSC and after prolonged standing, the stoichiometry was determined to be H₃CN(H)CSN(H)NH₂ + 3BrO₃^? → 2CO₂ + NH₄⁺ + SO₄^2? + N₂ + 3Br^? + H⁺ (A). An interim stoichiometry is also obtained in which one of the CO₂ molecules is replaced by HCOOH with an overall stoichiometry of 3H₃CN(H)CSN(H)NH₂ + 8BrO₃^? → CO₂ + NH₄⁺ + SO₄^2? + HCOOH + N₂ + 3Br^? + 3H⁺ (B). Stoichiometry A and B are not very different, and so mixtures of the two were obtained. Compared to other oxidations of thiourea‐based compounds, this reaction is moderately fast and is first order in both bromate and substrate. It is autocatalytic in HOBr. The reaction is characterized by an autocatalytic sigmoidal decay in the consumption of MTSC, while in excess bromate conditions the reaction shows an induction period before autocatalytic formation of bromine. In both cases, oxybromine chemistry, which involves the initial formation of the reactive species HOBr and Br₂, is dominant. The reactions of MTSC with both HOBr and Br₂ are fast, and so the overall rate of oxidation is dependent upon the rates of formation of these reactive species from bromate. Our proposed mechanism involves the initial cleavage of the C? N bond on the azo‐side of the molecule to release nitrogen and an activated sulfur species that quickly and rapidly rearranges to give a series of thiourea acids. These thiourea acids are then oxidized to the sulfonic acid before cleavage of the C? S bond to give SO₄^2?, CO₂, and NH₄⁺. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 237–247, 2002     

Study of the oxidation of ethylenediaminetetra-acetic acid with lead dioxide suspension in sulphuric acid

The stoichiometry of the reaction between lead dioxide suspension and EDTA was studied by derivative polarographic titration and determination of the products. Four moles of Pb(IV) are reduced per mole of EDTA with moderate speed at room temperature in sulphuric acid solutions. Four moles of carbon dioxide and 3 moles of formaldehyde are the products of the oxidation of 1 mole of EDTA. One mole of N-hydroxymethylethylenediamine is also thought to be produced. The overall reaction may be written as 4Pb(IV) + EDTA + 4H(2)O-->4Pb(II) + 4CO(2) + 3HCHO + H(2)NCH(2)CH(2)NHCH(2)OH + 8H(+). Ethylenediamine is also partly produced if a large excess of lead dioxide is used.     

Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of N-acetylthiourea by chlorite and chlorine dioxide

The oxidation reactions of N-acetylthiourea (ACTU) by chlorite and chlorine dioxide were studied in slightly acidic media. The ACTU-ClO(2)(-) reaction has a complex dependence on acid with acid catalysis in pH > 2 followed by acid retardation in higher acid conditions. In excess chlorite conditions the reaction is characterized by a very short induction period followed by a sudden and rapid formation of chlorine dioxide and sulfate. In some ratios of oxidant to reductant mixtures, oligo-oscillatory formation of chlorine dioxide is observed. The stoichiometry of the reaction is 2:1, with a complete desulfurization of the ACTU thiocarbamide to produce the corresponding urea product: 2ClO(2)(-) + CH(3)CONH(NH(2))C=S + H(2)O --> CH(3)CONH(NH(2))C=O + SO(4)(2-) + 2Cl(-) + 2H(+) (A). The reaction of chlorine dioxide and ACTU is extremely rapid and autocatalytic. The stoichiometry of this reaction is 8ClO(2)(aq) + 5CH(3)CONH(NH(2))C=S + 9H(2)O --> 5CH(3)CONH(NH(2))C=O + 5SO(4)(2-) + 8Cl(-) + 18H(+) (B). The ACTU-ClO(2)(-) reaction shows a much stronger HOCl autocatalysis than that which has been observed with other oxychlorine-thiocarbamide reactions. The reaction of chlorine dioxide with ACTU involves the initial formation of an adduct which hydrolyses to eliminate an unstable oxychlorine intermediate HClO(2)(-) which then combines with another ClO(2) molecule to produce and accumulate ClO(2)(-). The oxidation of ACTU involves the successive oxidation of the sulfur center through the sulfenic and sulfinic acids. Oxidation of the sulfinic acid by chlorine dioxide proceeds directly to sulfate bypassing the sulfonic acid. Sulfonic acids are inert to further oxidation and are only oxidized to sulfate via an initial hydrolysis reaction to yield bisulfite, which is then rapidly oxidized. Chlorine dioxide production after the induction period is due to the reaction of the intermediate HOCl species with ClO(2)(-). Oligo-oscillatory behavior arises from the fact that reactions that form ClO(2) are comparable in magnitude to those that consume ClO(2), and hence the assertion of each set of reactions is based on availability of reagents that fuel them. A computer simulation study involving 30 elementary and composite reactions gave a good fit to the induction period observed in the formation of chlorine dioxide and in the autocatalytic consumption of ACTU in its oxidation by ClO(2).     

Synthesis and characterization of nickel(II) bis(alkylthio)salen complexes

NiX2(2-RSC6H4CH=NCH2CH2N=CHC6H4SR-2) (NiX2L; L = 5) (1a, X = Br, R = C6H13; 1b, X = Cl, R = C12H25) and NiX2(2-C6H13SC6H4CH2NHCH2CH2NHCH2C6H4SC6H13-2) (NiX2L; L = 6) (2a, X = Br; 2b, X = Cl; 2c, X = OClO3) were prepared from ligands 5 and 6, respectively. The 1:2 metal-ligand complex Ni(OClO3)2(2-RSC6H4CH2NHCH2CH2NHCH2C6H4SR-2)2 3, was obtained from an EtOH solution of 2c. The characterization of paramagnetic 1-3 included single-crystal X-ray diffraction studies of 1a and 3. Complex 2c converted into 3 in the presence of excess ligand 6 in CHCl3.     

Uncatalyzed reactions in the classical Belousov-Zhabotinsky system. I. Reactions of bromomalonic acid with acidic bromate and with HOBr

The uncatalyzed reactions of bromomalonic acid (BrMA) with acidic bromate and with hypobromous acid were studied in 1 M sulfuric acid, a usual medium for the oscillatory Belousov-Zhabotinsky (BZ) reaction, by following the rate of the carbon dioxide evolution associated with these reactions. In addition, the decarboxylation rate of dibromomalonic acid (Br2MA) was also measured to determine the first-order rate constant of its decomposition (4.65 x 10(-5) s(-1) in 1 M H2SO4). The dependence of that rate constant on the hydrogen ion concentration suggests a carbocation formation. A slow oligomerization of BrMA observed in sulfuric acid solutions is also rationalized as a carbocationic process. The initial rate of the BrMA-BrO3- reaction is a bilinear function of the BrMA and BrO3- concentrations with a second-order rate constant of 3.8 x 10(-4) M(-1) s(-1). When a great excess of BrO3- is applied, then BrMA is oxidized mostly to CO2. A reaction scheme compatible with the experimental finding is also given. On the other hand, when less BrO3- and more organic substrate - BrMA or malonic acid (MA)--is applied, then addition reactions of various carbocations with the enol form of the organic substrates should be taken into account in later stages of the reaction. It was discovered that HOBr, which brominates BrMA to Br2MA when BrMA is in excess, can also oxidize BrMA when HOBr is in excess. As Br2MA does not react with HOBr, it is assumed that the acyl hypobromite, formed in the first step of the HOBr and BrMA reaction, can react with an additional HOBr to give oxidation products. It was found that the initial rate of the reaction can be described by the following experimental rate law: k(BHOB)[BrMA]0[HOBr]0(2), where k(BHOB) = 5 M(-2) s(-1). A reaction scheme for the oxidation of BrMA by HOBr is given for conditions where HOBr is in excess. Model calculations illustrate qualitatively that the suggested reaction schemes are able to mimic the experiments. (More quantitative simulations are prevented by kinetic data missing for the various carbocation intermediates.) Finally, the effects of these newly observed reactions on oscillatory BZ systems are discussed briefly.     

Dual control mechanism in a Belousov-Zhabotinskii (B-Z) oscillator with glucose and oxalic acid as a double substrate

Oscillations in a Belousov-Zhabotinskii (B-Z) system having oxalic acid (OA) and glucose (G) as a mixed organic substrate, neither of which acts as a bromine scavenger, have been investigated. Studies have been performed for (i) varying the concentration of G while keeping the OA concentration fixed and (ii) varying OA but keeping G fixed in a batch reactor. In both cases upper and lower critical limits occur, between which oscillations are observed. Both single and double frequency oscillations have been observed in a wide range of concentrations of G as well as of OA. The induction period in most of the cases was <1 min. When G is fixed and OA is varied, the time pause between the sequential oscillations increases with an increase in OA. On the other hand when OA is fixed and G is varied, the time-pause decreases with an increase in G. The first type of oscillation is Br(-)-controlled, whereas the second is non-Br(-)-controlled. The order of addition of G and OA in the last has no influence on the induction period. It influences, however, the oscillatory characteristics. Br(2) evolution in the G + OA + Ce(4+) + BrO(3)(-) + H(2)SO(4) reaction system has been investigated spectrophotometrically. ESR and polymerization studies indicate the important role of free radicals in influencing the reaction mechanism. A tentative dual control mechanism has been suggested involving autocatalysis of HBrO(2) and BrO2*.     

Cyclodextrin-aided determination of iodate and bromate in drinking water by microcolumn ion chromatography with precolumn enrichment.

A selective and simple method for the determination of iodate (IO3-) and bromate (BrO3-) by microcolumn ion chromatography (IC) is presented. In this study, IO3- and BrO3- were determined as IBr2- and tribromide (Br3-), respectively, via a postcolumn reaction with bromide (Br) under acidic conditions with the aid of alpha-cyclodextrin (alpha-CD) in microcolumn IC. IO3- and BrO3- were selectively detected by the present method at a wavelength of 253 or 265 nm. The present system achieved good selectivity for IO3- and BrO3- as well as good repeatability under suitable conditions. Precolumn enrichment improved the detection limit, and allowed the determination of BrO3- in bottled water as low as sub microg L(-1) level in microcolumn IC.     

Solid state structure and solution behaviour of organoselenium(II) compounds containing 2-{E(CH2CH2)2NCH2}C6H4 groups (E = O, NMe)

Cleavage of the Se-Se bond in [2-{O(CH(2)CH(2))(2)NCH(2)}C(6)H(4)](2)Se(2) (1) and [2-{MeN(CH(2)CH(2))(2)NCH(2)}C(6)H(4)](2)Se(2) (2) by treatment with SO(2)Cl(2), bromine or iodine (1 : 1 molar ratio) yielded [2-{O(CH(2)CH(2))(2)NCH(2)}C(6)H(4)]SeX [X = Cl (3), Br (4), I (5)] and [2-{MeN(CH(2)CH(2))(2)NCH(2)}C(6)H(4)]SeI (6). The compounds were characterized in solution by NMR spectroscopy (1H, 13C, 15N, 77Se, 2D experiments). The solid-state molecular structures of 1-3, 4.HBr, 5 and 6 were established by single crystal X-ray diffraction. In all cases T-shaped coordination geometries, i.e. (C,N)SeSe (1, 2), (C,N)SeX (3, 5, 6; X = halogen) or CSeBr(2) (4.HBr), were found. Supramolecular associations in crystals based on hydrogen contacts are discussed.     

Kinetic studies on the temperature dependence of the BrO + BrO reaction using laser flash photolysis

The BrO self-reaction, BrO + BrO → products (1), has been studied using laser flash photolysis coupled with UV absorption spectroscopy over the temperature range T = 266.5-321.6 K, under atmospheric pressure. BrO radicals were generated via laser photolysis of Br(2) in the presence of excess ozone. Both BrO and O(3) were monitored via UV absorption spectroscopy using charge-coupled device (CCD) detection. Simultaneous fitting to both temporal concentration traces allowed determination of the rate constant of the two channels of , BrO + BrO → 2Br + O(2) (1a); BrO + BrO → Br(2) + O(2) (1b), hence the calculation of the overall rate of and the branching ratio, α: k(1a)/cm(3) molecule(-1) s(-1) = (1.92 ± 1.54) × 10(-12) exp[(126 ± 214)/T], k(1b)/cm(3) molecule(-1) s(-1) = (3.4 ± 0.8) × 10(-13) exp[(181 ± 70)/T], k(1)/cm(3) molecule(-1) s(-1) = (2.3 ± 1.5) × 10(-12) exp(134 ± 185 /T) and α = k(1a)/k(1) = (0.84 ± 0.09) exp[(-7 ± 32)/T]. Errors are 1σ, statistical only. Results from this work show a weaker temperature dependence of the branching ratio for channel (1a) than that found in previous work, leading to values of α at temperatures typical of the Polar Boundary Layer higher than those reported by previous studies. This implies a shift of the partitioning between the two channels of the BrO self-reaction towards the bromine atom and hence directly ozone-depleting channel (1a).     

Determination of iodine and bromine compounds by ion chromatography/dynamic reaction cell inductively coupled plasma mass spectrometry.

An inductively coupled plasma mass spectrometer (ICP-MS) was used as an ion chromatographic detector for the speciation of iodine and bromine. Gradient elution using NH4NO3 at pH 10 allowed the chromatographic separation of ionic iodine (I- and IO3-) and bromine (Br- and BrO3-) species in less than 8 min. Effluents from the ion-exchange column were delivered to the nebulization system of ICP-MS for the determination of I and Br. The potentially interfering 38Ar40ArH+ and 40Ar40ArH+ at the bromine masses m/z 79 and 81 were significantly reduced in intensity (by approximately two orders of magnitude) by using 0.6 mL min(-1) O2 as a reactive cell gas in the dynamic reaction cell (DRC). Moreover, the signal-to-background ratio at iodine mass m/z 127 increased significantly when O2 was used as the reaction gas. The detection limits were in the range of 0.001-0.002 and 0.03-0.04 ng mL(-1) for various I and Br compounds, respectively, based on the peak height. The relative standard deviation of the peak areas for five injections of a 2 ng mL(-1) I-, IO3- and 20 ng mL(-1) Br-, BrO3- mixture was in the range of 3-4%. The concentrations of I and Br compounds have been determined in selected water and urine samples. The spike recoveries were in the range of 94-102% for all of the determinations. This method has also been applied to determine various I and Br compounds in an NIST RM 8435 whole-milk powder reference material and a seaweed sample obtained locally. A microwave-assisted extraction method was used to extract these compounds, which were quantitatively leached with a 10% mass/volume (m/v) tetramethylammonium hydroxide (TMAH) solution in a focused microwave field within a period of 6 min. The major components of I and Br in milk powder and seaweed were I- and Br-.     

丝氨酸-BrO^-~3-Mn^2^+-H2SO4体系振荡反应的研究

首次报道了间歇釜中以丝氨酸(Ser)-BrO^-~3-Mn^2^+-H2SO4为体系(简称Ser-BZ体系)的新型BZ类振荡反应,其特征如下：(1)虽然Ser不能发生溴代反应,但即使在无丙酮或惰性气体流时也能在间歇釜中观察到持续振荡;(2)振荡诱导期极短(～0),振荡次数较少(<11次);(3)振荡反应受到Cl^-,Br^-,丙烯腈等的抑制;但当加入足够量Ag^+使[Br^-]的振荡抑制后,仍可在Pt电极上观察到振荡现象。根据上述特征和反应产物分析,推测Ser-BZ振荡反应可能是自由基-控制模型,而非Br^--控制模型。加入适量丙酮可诱导连续振荡反应,归因于两种控制模型的共存。通过对Mn^3^+-Ser和BrO^-~3-Mn^2^+反应的动力学研究,并结合FKN机理,对Ser-BZ振荡反应机理进行了初步讨论。     

The source of the carbon monoxide in the classical Belousov-Zhabotinsky reaction

CO and CO2 evolution was measured in a cerium and in a ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction. These gases were stripped from the reaction mixture by a N2 carrier gas, mixed with H2, converted to methane on a Ni catalyst, and then measured by a flame ionization detector (FID). CO could be detected separately by absorbing CO2 on a soda lime column. In separate experiments it was proven that CO is produced in a reaction of BrO2* radicals with bromomalonic acid (BrMA). To this end BrO2(.-) radicals were generated in two different ways: (i) in the reaction HBrO2 + HBrO3 <--> 2 BrO2(.-) + H2O and (ii) by reducing HBrO3 to BrO2(.-) by Fe(2+). It was found that (.-)OH radicals--produced by Fenton's reagent--can also generate CO from BrMA. We propose that CO can be formed when an inorganic radical (like BrO2(.-) or (.-)OH) reacts with the enol form of BrMA producing an acyl radical which decarbonylates in the next step. Malonic acid (MA)-BrMA mixtures were prepared by a new method modifying Zaikin and Zhabotinsky's original recipe to minimize the production of dibromomalonic acid (Br2MA).     

Kinetics and mechanism of oxidation of secondary alcohols by potassium bromate

The oxidation by Br(V) of propan-2-ol follows the rate law (?d[Br(V)]/dt) = k₄ [alcohol][Br(V)][H⁺]². The initial reaction is complicated by the presence of the product bromide ion. The reaction is composed of two second order reactions—the first, a comparatively slow one and the second stage, a faster reaction which is mainly bromine oxidation. The pure bromate oxidation can be followed by the initial addition of mercuric acetate which prevents the accumulation of bromine in the system under these conditions. The reaction rate does not depend on the nature and structure of the alcohol. A mechanism involving a slow rate-determining formation of an alkyl-bromate ester followed by a fast decomposition to the products is in accord with the observed results.     

Synthesis and structural characterization of mono- and bisfunctional o-carboranes

Functionalized o-carboranes are interesting ligands for transition metals. Reaction of LiC2B10H11 with Me2NCH2CH2Cl in toluene afforded 1-Me2NCH2CH2-1,2-C2B10H11 (1). Treatment of 1 with 1 equiv. of n-BuLi gave [(Me2NCH2CH2)C2B10H10]Li ([1]Li), which was a very useful synthon for the production of bisfunctional o-carboranes. Reaction of [1]Li with RCH2CH2Cl afforded 1-Me2NCH2CH2-2-RCH2CH2-1,2-C2B10H10 (R = Me2N (2), MeO (3)). 1 and 2 were also prepared from the reaction of Li2C2B10H10 with excess Me2NCH2CH2Cl. Treatment of [1]Li with excess MeI or allyl bromide gave the ionic salts, [1-Me3NCH2CH2-2-Me-1,2-C2B10H10][I] (4) and [1-Me2N(CH2=CHCH2)CH2CH2-2-(CH2=CHCH2)-1,2-C2B10H10][Br] (6), respectively. Interaction of [1]Li with 1 equiv. of allyl bromide afforded 1-Me2NCH2CH2-2-(CH2=CHCH2)-1,2-C2B10H10 (5). Treatment of [1]Li with excess dimethylfulvene afforded 1-Me2NCH2CH2-2-C5H5CMe2-1,2-C2B10H10 (7). Interaction of [1]Li with excess ethylene oxide afforded an unexpected product 1-HOCH2CH2-2-(CH2=CH)-1,2-C2B10H10 (8). 1 and 3 were conveniently converted into the corresponding deborated compounds, 7-Me2NHCH2CH2-7,8-C2B9H11 (9) and 7-Me2NHCH2CH2-8-MeOCH2CH2-7,8-C2B9H10 (10), respectively, in MeOH-MeOK solution. All of these compounds were characterized by various spectroscopic techniques and elemental analyses. The solid-state structures of 4 and 6-10 were confirmed by single-crystal X-ray analyses.     

含氮原子桥联吡咯基稀土金属双核配合物的合成及催化ε-己内酯的开环聚合反应

RE(CH2SiMe3)3(THF)2和1.5 equiv.(C4H3NHCH2)2NCH3(1)反应合成得到含氮原子桥联吡咯基稀土金属双核配合物[η1∶η1∶η1-(C4H3NCH2)2NCH3]RE{μ-η5∶η5∶η1-(C4H3NCH2)2NCH3}RE[η1∶η1∶η1-(C4H3NCH2)2NCH3](THF)[RE=Y(2),Er(3),Yb(4)],所得配合物经过核磁共振、红外和元素分析表征,配合物2和4经单晶X-Ray进一步确认结构.同时研究了稀土配合物作为单一组分催化剂催化ε-内酯的开环聚合反应.     

Uncatalyzed reactions in the classical Belousov-Zhabotinsky system. 2. The malonic acid-bromate reaction in acidic media

The title reaction was studied with various techniques in 1 M sulfuric acid, a usual medium for the oscillatory Belousov-Zhabotinsky (BZ) reaction. It was found to be a more complex process than the bromomalonic acid (BrMA)-BrO3- reaction studied previously in the first part of this work. Malonic acid (MA) can react with acidic bromate by two parallel mechanisms. The main aim of the present research was to determine the mechanisms, the rate laws, and the rate constants for these parallel channels. In one reaction channel the first molecular products are glyoxalic acid (GOA) and CO2 while in the other channel mesoxalic acid (MOA) is the first molecular intermediate, that is, no CO2 is formed in this step. To prove these two independent routes specific colorimetric techniques were developed to determine GOA and MOA selectively. The rate of the GOA channel was determined by following the rate of the carbon dioxide evolution characteristic for this reaction route. In this step, regarding it as an overall process, one MA is oxidized to GOA and CO2 and one BrO3- is reduced to HOBr, which forms BrMA with another MA. The initial rate of the GOA channel is a bilinear function of the initial MA and BrO3- concentrations with a second-order rate constant k(GOA)= 2.4 x 10(-7) M(-1) s(-1). The rate of the other channel was calculated from the rate of the BrO3- consumption measured in separate experiments, assuming that the measured depletion is a sum of two separate terms reflecting the consumptions due to the two independent channels. In the MOA channel one MA is oxidized to MOA and one BrO3- is consumed while another MA is brominated as in the GOA channel. It was found that the initial rate of the MOA channel is also a bilinear function of the MA and BrO3- concentrations with a second-order rate constant k(MOA)= 2.46 x 10(-6) M(-1) s(-1). Separate chemical mechanisms are suggested for both channels. In all of the various bromate-substrate reactions of these mechanisms oxygen atom transfer from the bromate to the substrate occurs generating bromous acid intermediate. This can be of high importance in BZ systems as bromous acid is the autocatalytic intermediate there. GOA and MOA also can be oxidized by acidic bromate but a study of these reactions will be published later.